Manufacturing method for polyphenol composition

ABSTRACT

A method for producing a polyphenol composition including a step of subjecting (A) a hardly water-soluble polyphenol and (B) one or more selected from cathechins, chlorogenic acids and methylated compounds of hardly water-soluble polyphenols to a heat treatment at from 100 to 180° C. in the presence of an aqueous medium.

CROSS REFERENCE TO RELATED APPLICATION

This application is a 371 of PCT/JP2011/063098, filed on Jun. 8, 2011,and claims priority to the following Japanese Patent Applications: JP2010-131816 filed on Jun. 9, 2010; and JP 2010-226574, filed on Oct. 6,2010.

FIELD OF THE INVENTION

The present invention relates to a method for producing a poly phenolcomposition having an excellent solubility to water.

BACKGROUND OF THE INVENTION

Recently, various materials having a physiological function have beenproposed, and many health foods containing these materials have beencommercialized. Among them, polyphenols are known to have anantioxidative activity and are acknowledged as an important component ofthe health foods because of their expected effects such asantiarteriosclerotic, antiallergic and bloodstream enhancement effects.

However, since many polyphenols are hardly soluble to water, it isdifficult to use them for aqueous foods such as soft drinks.

Hesperidin, which is a kind of flavonoids and also referred to asvitamin P, is known to be contained in a large amount in the peel of thecitrus plants. Hesperidin is widely used for foods, pharmaceuticals orthe like, because of its various physiological functions such asenhancement of capillaryvessel, prevention of bleeding and regulation ofblood pressure. However, although hesperidin dissolves in an alkalineaqueous solution, it hardly dissolves in a neutral to acidic aqueoussolution. For example, its solubility in water at 25° C. is as low as0.02 mg/g.

Then, a technique to solve this problem has been investigated, includinga proposal for α-glucosylhesperidin obtained by binding glucose tohesperidin (Patent Document 1). The solubility of α-glucosylhesperidinin water at 25° C. is as high as 200 mg/g or more and it has someadvantages such as a function similar to hesperidin.

On the other hand, techniques to solubilize a hardly water-solublepolyphenol into water have been investigated, and various methods havebeen proposed, including a method for solubilizing the flavonoidcompound contained therein by adding a hesperidin glycoside to citrusjuice and fruit juice drink followed by heating the mixture (PatentDocument 2); a method for making a clathrate of a hardly water-solubleflavonoid and β-cyclodextrin by a heat treatment of them followed byadding α-glucosylhesperidin thereto (Patent Document 3); and a methodfor solubilizing the flavonoid by mixing a hardly soluble flavonoid andsoybean saponin and/or malonyl isoflavon glycoside in an aqueous mediumfollowed by a heat treatment (Patent Document 4). In these methods, theheat treatment of the hardly water-soluble polyphenols is carried out ataround from 70° C. to 90° C.

PRIOR ART DOCUMENT Patent Document

-   [Patent Document 1] Japanese Patent No. 3549436-   [Patent Document 2] JP-A 2000-236856-   [Patent Document 3] JP-A 2008-271839-   [Patent Document 4] WO-A 2005/003112

SUMMARY OF THE INVENTION

The present invention relates to the following items (1) to (42).

(1) A method for producing a polyphenol composition containing a step ofsubjecting (A) a hardly water-soluble polyphenol and (B) one or moreselected from the catechins, chlorogenic acids and methylated compoundsof hardly water-soluble polyphenols to a heat treatment at from 100 to180° C. in the presence of an aqueous medium.

(2) The method for producing the polyphenol composition mentioned above,wherein the log P value of (A) the hardly water-soluble polyphenol isfrom −1.0 to 4.0.

(3) The method for producing the polyphenol composition mentioned above,wherein the log P value of (A) the hardly water-soluble polyphenol isfrom −0.5 to 3.5.

(4) The method for producing the polyphenol composition mentioned above,wherein (A) the hardly water-soluble polyphenol is one or more selectedfrom hesperidin, quercetin, resveratrol, naringin, curcumin, rutin,caffeic acid and ferulic acid.

(5) The method for producing the polyphenol composition mentioned above,wherein a mass ratio (A)/(B) of (A) the hardly water-soluble polyphenolto (B) one or more selected from the catechins, chlorogenic acids andmethylated compounds of hardly water-soluble polyphenols is from 0.005to 10 in the step of the heat treatment.

(6) The method for producing the polyphenol composition mentioned above,wherein the mass ratio (A)/(B) of (A) the hardly water-solublepolyphenol to (B) one or more selected from the catechins, chlorogenicacids and methylated compounds of hardly water-soluble polyphenols isfrom 0.01 to 10 in the step of the heat treatment.

(7) The method for producing the polyphenol composition mentioned above,wherein the mass ratio (A)/(B) of (A) the hardly water-solublepolyphenol to (B) one or more selected from the catechins, chlorogenicacids and methylated compounds of hardly water-soluble polyphenols isfrom 0.02 to 3 in the step of the heat treatment.

(8) The method for producing the polyphenol composition mentioned above,wherein the mass ratio (A)/(B) of (A) the hardly water-solublepolyphenol to (B) one or more selected from the catechins, chlorogenicacids and methylated compounds of hardly water-soluble polyphenols isfrom 0.168 to 2.33 in the step of the heat treatment.

(9) The method for producing the polyphenol composition mentioned above,wherein the methylated compound of the hardly water-soluble polyphenolis methylhesperidin.

(10) The method for producing the polyphenol composition mentionedabove, further containing a step of cooling the reaction solutionobtained by the heat treatment and a step of removing solid from thecooled reaction solution.

(11) A polyphenol composition obtained by the producing method mentionedabove.

(12) A method for producing a hesperidin composition containing a stepof subjecting hesperidin and hesperidin sugar adduct to a heat treatmentat from 100 to 180° C. in the presence of an aqueous medium.

(13) The method for producing the hesperidin composition mentionedabove, wherein the hesperidin sugar adduct is glucosylhesperidin.

(14) The method for producing the hesperidin composition mentionedabove, wherein the hesperidin sugar adduct is monoglucosylhesperidin.

(15) The method for producing the hesperidin composition mentionedabove, wherein a mass ratio of hesperidin to hesperidin sugar adduct isfrom 0.1 to 20 in the step of the heat treatment.

(16) The method for producing the hesperidin composition mentionedabove, wherein the mass ratio of hesperidin to hesperidin sugar adductis from 0.2 to 15 in the step of the heat treatment.

(17) The method for producing the hesperidin composition mentionedabove, wherein the mass ratio of hesperidin to hesperidin sugar adductis from 0.2 to 10 in the step of the heat treatment.

(18) The method for producing the hesperidin composition mentionedabove, wherein the mass ratio of hesperidin to hesperidin sugar adductis from 0.3 to 5 in the step of the heat treatment.

(19) The method for producing the hesperidin composition mentionedabove, wherein the mass ratio of hesperidin to hesperidin sugar adductis from 1.22 to 3 in the step of the heat treatment.

(20) The method for producing the hesperidin composition mentionedabove, wherein the aqueous medium is water or an aqueous solutioncontaining alcohol having 4 or less carbon atoms.

(21) The method for producing the hesperidin composition mentionedabove, further containing a step of cooling the reaction solutionobtained by the heating treatment and a step of removing solid from thecooled reaction solution.

(22) The method for producing the hesperidin composition mentionedabove, wherein the cooling rate from the heating temperature to 90° C.is 0.1° C./s or more in the step of cooling the reaction solution.

(23) The method for producing the hesperidin composition mentionedabove, wherein the cooling rate from the heating temperature to 90° C.is 0.2° C./s or more in the step of cooling the reaction solution.

(24) The method for producing the hesperidin composition mentionedabove, wherein the cooling rate from the heating temperature to 90° C.is 0.5° C./s or more in the step of cooling the reaction solution.

(25) The method for producing the hesperidin composition mentionedabove, wherein the cooling rate from the heating temperature to 90° C.is 1° C./s or more in the step of cooling the reaction solution.

(26) The method for producing the hesperidin composition mentionedabove, wherein the cooling rate from the heating temperature to 90° C.is 3° C./s or more in the step of cooling the reaction solution.

(27) The method for producing the hesperidin composition mentionedabove, wherein the cooling rate from the heating temperature to 90° C.is 5° C./s or more in the step of cooling the reaction solution.

(28) The method for producing the hesperidin composition mentionedabove, wherein the cooling rate from the heating temperature to 90° C.is 100° C./s or less in the step of cooling the reaction solution.

(29) The method for producing the hesperidin composition mentionedabove, wherein the cooling rate from the heating temperature to 90° C.is 50° C./s or less in the step of cooling the reaction solution.

(30) The method for producing the hesperidin composition mentionedabove, wherein a form of the hesperidin composition is an aqueoussolution or a powder.

(31) A hesperidin composition wherein a mass ratio of hesperidin tohesperidin sugar adduct is from 0.3 to 10.

(32) The hesperidin composition mentioned above, wherein the mass ratioof hesperidin to hesperidin sugar adduct is from 0.4 to 8.

(33) The hesperidin composition mentioned above, wherein the mass ratioof hesperidin to hesperidin sugar adduct is from 0.5 to 8.

(34) The hesperidin composition mentioned above, wherein the mass ratioof hesperidin to hesperidin sugar adduct is from 1 to 5.

(35) The hesperidin composition mentioned above, wherein a solubility ofhesperidin to water at 25° C. is 1.3 g/L or more.

(36) The hesperidin composition mentioned above, wherein the solubilityof hesperidin to water at 25° C. is 2 g/L or more.

(37) The hesperidin composition mentioned above, wherein the solubilityof hesperidin to water at 25° C. is 3 g/L or more.

(38) The hesperidin composition mentioned above, wherein the solubilityof hesperidin to water at 25° C. is 5 g/L or more.

(39) The hesperidin composition obtained by the producing methodmentioned above, wherein a mass ratio of hesperidin to hesperidin sugaradduct is from 0.3 to 10.

(40) The hesperidin composition obtained by the producing methodmentioned above, wherein the mass ratio of hesperidin to hesperidinsugar adduct is from 0.4 to 8.

(41) The hesperidin composition obtained by the producing methodmentioned above, wherein the mass ratio of hesperidin to hesperidinsugar adduct is from 0.5 to 8.

(42) The hesperidin composition obtained by the producing methodmentioned above, wherein the mass ratio of hesperidin to hesperidinsugar adduct is from 1 to 5.

Embodiment for Carrying out the Invention

A production process of hesperidin glycoside such asα-glucosylhesperidin is complex and expensive. Therefore, it is noteconomically favorable to use hesperidin glycoside in place ofhesperidin or as a solubilizing agent. In addition, use of asolubilizing agent such as malonyl isoflavon glycoside may cause aproblem of limited application due to a peculiar grain smell of thesolubilizing agent derived from soy bean, although a solubility ofhardly water-soluble polyphenol may be increased. Furthermore, only thehesperidin composition with low content of hesperidin has been obtained,and the method for sufficiently dissolving hesperidin has not been knownyet.

Thus, the present invention relates to providing a method for producinga polyphenol composition having an excellent solubility to water using amaterial with low cost and less influence on the taste and flavor of thecomposition.

In addition, the present invention relates to providing a hesperidincomposition having a high content of hesperidin and the excellentsolubility, as well as a method for producing the hesperidincomposition.

As a result of extensive investigation on the solubilizing technique forhardly water-soluble polyphenols, the present inventors found that thesolubility of hardly water-soluble polyphenols drastically increases byheating the hardly water-soluble polyphenols and the catechins,chlorogenic acids or a methylated product of hardly water-solublepolyphenols at 100° C. or higher in the presence of an aqueous medium,and that the composition subjected to this treatment suppresses theprecipitation of the hardly water-soluble polyphenols and maintains highsolubility even at room temperature. Furthermore, the inventors foundthat the influence of the catechins, chlorogenic acids or the methylatedproduct of hardly water-soluble polyphenols on the taste and flavor ofthe composition is small.

Furthermore, as a result of extensive investigation on the solubilizingtechnique for hesperidin, the present inventors have found that thesolubility of hesperidin drastically increases by heating hesperidin andhesperidin sugar adduct at 100° C. or higher in the presence of anaqueous medium, and that the composition subjected to this treatmentsuppresses the precipitation of hesperidinand maintains high solubilityof hesperidin even at room temperature.

According to the present invention, a polyphenol composition having theexcellent solubility to water can be provided at low cost. Thepolyphenol composition of the present invention is useful for variousfoods and drinks and pharmaceuticals because the influence of thesolubilizing agent on the taste and flavor is small.

Furthermore, according to the present invention, the solubility ofhesperidin to water or the like can be increased and the hesperidincomposition having the excellent solubility regardless of high contentof hesperidin can be provided.

The method for producing the polyphenol composition according to thepresent invention includes the step of subjecting (A) a hardlywater-soluble polyphenol and (B) one or more selected from cathechins,chlorogenic acids and methylated compounds of hardly water-solublepolyphenols to a heat treatment at from 100 to 180° C. in the presenceof an aqueous medium. Hereafter, “one or more selected from thecatechins, chlorogenic acids and methylated compounds of hardlywater-soluble polyphenols” is also simply referred to as a component“B”. The method for producing the polyphenol composition is alsoreferred to as the first method.

The term “hardly water-soluble polyphenols” herein means the polyphenolshaving a log P value of from −1.0 to 4.0. The hardly water-solublepolyphenols preferably have a log P value of from −0.5 to 3.5. The log Pvalue is a common logarithm of the partition coefficient between1-octanol, and water and an index indicative of a hydrophobicity of anorganic compound. Larger positive log P value indicates largerhydrophobicity. The log P value of the polyphenols may be measuredaccording to the flask shaking method in accordance with JIS Z7260-107.The details are described in Examples.

Preferably applicable (A) hardly water-soluble polyphenols includephenolic substances having one or more, or in particular two or morehydroxyl groups connected to a benzene ring, for example, a flavonoidderived from plant, tannin, phenolic acid or the like. Examples of thehardly water-soluble polyphenols more preferably applicable includeflavonols, flavanones, flavones, isoflavones, phenol carboxylic acids orthe like.

Specific examples include rutin, quercitrin, isoquercitrin, quercetin,myricitrin, daidzein, daidzin, glycitein, glycitin, genistein, genistin,myricetin, hesperidin, neohesperidin, hesperetin, naringin, curcumin,ringenin, prunin, astragalin, kaempferol, resveratrol, apiin, apigenin,delphinidin, delphin, nasunin, peonidin, peonin, petunin, malvidin,malvin, enin, cyanidin, leukocyanidin, cyanine, chrysanthemine,keracyanin, idaein, mecocyanin, pelargonidin, callistephin, caffeicacid, ferulic acid, p-coumaric acid or the like. Among them, rutin,quercetin, hesperidin, naringin, curcumin, resveratrol, caffeic acid andferulic acid are preferable. The hardly water-soluble polyphenols may bea single substance or a mixture of two or more substances.

The catechins used in the present invention is a generic term, whichencompasses non-epi-form catechins such as catechin, gallocatechin,catechin gallate and gallocatechin gallate, and epi-form catechins suchas epicatechin, epigallocatechin, epicatechin gallate andepigallocatechin gallate. A content of the catechins is defined based onthe total amount of 8 types mentioned above.

As the catechins, a tea extract may be used. As the tea extract, atleast one selected from tea extract solution, the concentrate thereofand the purified product thereof may be used.

The “tea extract solution” herein means the extract solution from tealeaves with a hot water or a water-soluble organic solvent, neitherconcentrated nor purified. As the water-soluble organic solvent, forexample, lower alcohols such as ethanol may be used. As the extractionmethod, known methods such as kneader extraction, stirring extraction(batch extraction), counter-current extraction (drip extraction), columnextraction or the like may be used.

Tea leaves used for extraction may be roughly classified into anon-fermented tea, a semi-fermented tea and a fermented tea depending onthe processing method. As the non-fermented tea, green tea such assencha, bancha, gyokuro, tencha, kamairicha, kukicha, boucha, mecha, isexemplified. As the semi-fermented tea, oolong tea such as tekkannon,shikishu, golden cassia, wuyi rock tea, is exemplified. Further, asfermented tea, black teas such as Darjeeling, Assam and Ceylon isexemplified. These teas may be used either singly or in combination oftwo or more. Of these, green teas are preferred from the standpoint ofthe content of the catechins.

The term “concentrate of tea extract solution” means one obtained, froma solution which has been extracted from tea leaves selected fromnon-fermented tea, semi-fermented tea and fermented tea with hot wateror a water-soluble organic solvent, with the catechins at aconcentration raised by removing a part of water, and can be prepared,for example, by the method disclosed in JP-A-59-219384, JP-A-04-020589,JP-A-05-260907, JP-A-05-306279 or the like. The form thereof includessolid, aqueous solution, slurry or the like. Commercial products of theconcentrated tea extract solution may be used, including, theconcentrated green tea extract solution such as “POLYPHENON” (product ofMitsui Norin Co., Ltd.), “TEAFURAN” (product of ITO EN, LTD.),“SUNPHENON” (product of Taiyo Kagaku Co., Ltd.).

A purification of the tea extract solution or the like may be carriedout using a solvent and a column.

Chlorogenic acids used in the present invention is a generic term, whichcollectively encompasses monocaffeoylquinic acids including3-caffeoylquinic acid, 4-caffeoylquinic acid and 5-caffeoylquinic acid,monoferuloylquinic acids including 3-feruloylquinic acid,4-feruloylquinic acid and 5-feruloylquinic acid and dicaffeoylquinicacids including 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid and4,5-dicaffeoylquinic acid. A content of chlorogenic acids is definedbased on the total amount of 9 types mentioned above.

In addition, chlorogenic acids may be in the form of a salt including,for example, a salt with an alkaline metal such as sodium, potassium, asalt with an alkaline earth metal such as magnesium, calcium, a saltwith an organic amine such as monoethanolamine, diethanolamine,triethanolamine, and a salt with a basic amino acid such as arginine,lysine, histidine, ornithine.

As chlorogenic acids, the plant extract containing this, the concentratethereof, the purified product thereof or the like may be used. As suchplant extract, for example, extract from sunflower seed, unripe applefruit, green coffee bean, simon leaves, strobile of pine family plant,seed husk of pine family plant, leaves of sugarcane nandina, burdock,peel of eggplant, fruit of Japanese plum, coltsfoot, vitaceae familyplant or the like is exemplified. Among them, green coffee bean extractis preferable in view of a content of chlorogenic acids or the like. Asfor the kind of coffee tree, any of Coffee Arabica, Coffee Robusta,Coffee Liberica and Coffee Arabusta may be used. Methods and conditionsfor extraction, concentration and purification are not particularlylimited, and known methods and conditions may be used.

As the chlorogenic acids, commercially available chlorogenicacid-containing preparation such as, for example, Flavor Holder RC (T.Hasegawa Co., Ltd.) may also be used.

The methylated product of the hardly water-soluble polyphenols used inthe present invention is obtained by methylation of the hardlywater-soluble polyphenols mentioned above to solubilize it in water. Aposition and a number of the methylation are not particularly limited.Specifically, methylhesperidin, methylquercetin, methylresveratrol,methylrutin or the like are exemplified, among which methylhesperidin ispreferable. It is known that methylhesperidin mainly includeschalcone-type compound (A) and flavanone-type compound (B). As itsstructural component, the following are exemplified.

(wherein R represents a hydrogen atom or a methyl group.)

It is noted that methylhesperidin as a pharmaceutical additive and afood additive is mainly used as a mixture of the compound (C) andcompound (D).

(C) R Gl-2 Rh-2 (C-1) Me Me₂ H (C-2) H Me H (C-3) H H H

(D) R Gl-2 Rh-2 (D-1) H Me Me (D-2) H Me H (D-3) H H H(wherein G1 and Rh represent a glucose residue and a rhamnose residue,respectively. G1-2 and Rh-2 represent 2-position of the glucose residue(In the case of C-1,3-position is also included.) and 2-position of therhamnose residue, respectively.)

Hesperidin methylchalcone as a raw material for cosmetics is used as acompound represented by (E). It is noted that the composition whichcontains a large amount of chalcone type compound is also referred to ashesperidin methylchalcone.

(wherein R represents a hydrogen atom or a methyl group.)

Methylhesperidin used in the present invention may contain both of thechalcone-type compound (A) and the flavanone-type compound (B) mentionedabove or may contain either of them.

A more preferable methylhesperidin in the present invention is a mixtureof the compound (C) and the compound (D).

Methylhesperidin may be produced in accordance with a commonly knownmethod, for example, by dissolving hesperidin in an aqueous solution ofsodium hydroxide, allowing the alkaline solution thereof to react with acorresponding amount of dimethylsulfuric acid, neutralizing the reactionsolution with sulfuric acid, extracting the mixture with n-butylalcohol, and evaporating the solvent therefrom, followed byrecrystallization using isopropyl alcohol (Sakieki, Nippon Kagaku Zassi,79, 733-6 (1958)). The production method is not limited to this one.

A commercially available methylhesperidin-containing preparation may beused as methylhesperidin, including, for example, “Methyl hesperidin”(Tokyo Chemical Industry Co., Ltd.), “Hesperidin methylchalcone” (SigmaCo.) and “Methylhesperidin” (Hamari Chemicals Ltd.).

In the present invention, the catechins, chlorogenic acids or methylhesperidin may be used alone or in combination of two or more as thecomponent (B).

The production method of the hesperidin composition according to thepresent invention includes the step of subjecting hesperidin andhesperidin sugar adduct to a heat treatment at from 100 to 180° C. inthe presence of an aqueous medium. This producing method of thehesperidin composition is also referred to as the second method.

Hesperidin is a compound in which rutinose (L-rhamnosyl(α1->6)-D-glucose) is connected to a hydroxyl group at 7-position ofhesperetin (5,7,3′-trihydroxy-4′-methoxyflavanone) via a β-bonding.

Hesperidin sugar adduct is a compound composed of hesperidin with from 1to 10 sugars further bonded. Examples of the sugar include glucose,maltose, fructose, rhamnose, lactose or the like. Among them,glucosylhesperidin composed of hesperidin with from 1 to 10 glucoseunits bonded is preferable in view of its solubility and solubilizingpower, monoglucosylhesperidin with one glucose unit bonded being morepreferable. In addition, a number of glucose added may have adistribution. Preferred average mole number of glucose added relative to1 mole of hesperidin is from 1 to 10. It should be noted that hesperidinitself is a glycoside of hesperetin as an aglycone with sugar bonded asmentioned above. In order to distinguish from this in the presentinvention, the compound of hesperidin with sugar further bonded isreferred to as hesperidin sugar adduct.

These hesperidin and hesperidin sugar adduct may be industriallyproduced by a commonly known method utilizing a chemical synthesis andan enzymatic reaction. In addition, hesperidin may be obtained by anextraction from a natural product containing this, preferably from aplant. These substances are also manufactured and sold as a reagent orthe like. Examples of the commercially available hesperidin includeHesperidin “Hamari” from Hamari Chemicals Ltd. Examples of thecommercially available hesperidin sugar adduct include “HayashibaraHesperidin S” from Hayashibara Biochemical Laboratories, Inc.

The aqueous medium used in the present invention includes water and anaqueous solution of an organic solvent. Tap water, distilled water, ionexchange water and purified water are exemplified as water. The organicsolvent is not particularly limited so long as the solvent ishomogeneously mixed with water. As the organic solvent, an alcoholhaving 4 or less carbon atoms is preferable, methanol and ethanol beingmore preferable, and ethanol being even more preferable because it isapplicable for food. A concentration of the organic solvent in theaqueous solution is preferably from 0.1 to 80 mass % (hereafter simplydenoted by “%”), more preferably from 1 to 70%, more preferably from 5to 60%, even more preferably from 20 to 50%.

It is preferable to use an aqueous solution of an organic solvent as theaqueous medium because the content of hesperidin in the hesperidincomposition obtained may be increased.

In addition, the aqueous medium used in the present invention maycontain a solute. The solute is not particularly limited, and an acidsuch as amino acid, an inorganic salt, an organic salt, sugar or thelike may be exemplified. Soy sauce, ponzu sauce, basting, fruit juice,vegetable juice, coffee, tea or the like may be used.

Since the solubility of (A) hardly water-soluble polyphenols to water islow, it is preferable to disperse this into the aqueous medium to existin the form of slurry.

The content of (A) hardly water-soluble polyphenols in the aqueousmedium in the first method depends on a type of the hardly water-solublepolyphenols. Usually, it is preferably from 0.1 to 100 g/L, morepreferably from 0.5 to 50 g/L, more preferably from 0.7 to 20 g/L, evenmore preferably from 0.72 to 10 g/L in view of fluidity.

On the other hand, the component (B) of the present invention is usedpreferably as solution thereof in an aqueous medium. A content of thecomponent (B) in the aqueous medium is preferably from 0.1 to 200 g/L,more preferably from 0.5 to 100 g/L, more preferably from 1 to 50 g/L,even more preferably from 4.28 to 4.31 g/L in view of fluidity.

In the first method, a mass ratio ((A)/(B)) of (A) hardly water-solublepolyphenols to the component (B) in the aqueous medium is preferablyfrom 0.005 to 10, more preferably from 0.01 to 10, more preferably from0.02 to 3, even more preferably from 0.168 to 2.33 in view of solubilityof the polyphenol composition obtained after heat treatment and cooling.

A content of hesperidin in the aqueous medium in the second method ispreferably from 0.1 to 100 g/L, more preferably from 0.5 to 50 g/L, morepreferably from 1 to 20 g/L, even more preferably from 4 to 18 g/L inview of fluidity.

Hesperidin sugar adduct is used preferably in as a solution thereof inan aqueous medium. A content of hesperidin sugar adduct in the aqueousmedium is preferably from 0.1 to 200 g/L, more preferably from 0.5 to100 g/L, more preferably from 1 to 50 g/L, even more preferably from 5to 20 g/L in view of fluidity.

In the second method, a mass ratio of hesperidin to hesperidin sugaradduct in the aqueous medium is preferably from 0.1 to 20, morepreferably from 0.2 to 15, more preferably from 0.2 to 10, morepreferably from 0.3 to 5, even more preferably from 1.22 to 3 in view ofsolubility of the hesperidin composition obtained after heat treatmentand cooling.

The method of subjecting (A) hardly water-soluble polyphenols and thecomponent (B) to a heat treatment, and the method of subjectinghesperidin and hesperidin sugar adduct to a heat treatment in thepresence of an aqueous medium are not particularly limited, and acommonly known method may be applied.

A temperature of heat treatment is from 100 to 180° C., more preferablyfrom 110 to 170° C., more preferably from 120 to 160° C., even morepreferably from 120 to 150° C. in view of an enhancement of solubilityand a heat stability of the hardly water-soluble polyphenols. Heatingmeans include, for example, steam and electricity.

A pressure for the heat treatment is preferably from 0 to 10 MPa ingauge pressure, more preferably from 0.1 to 8 MPa, more preferably from0.1 to 6 MPa, more preferably from 0.2 to 6 MPa, more preferably from0.2 to 4 MPa, more preferably from 0.25 to 2 MPa, more preferably from0.3 to 1.5 MPa, even more preferably from 0.3 to 0.6 MPa. The pressureis preferably set at the saturated vapor pressure of water or higher.Gas may be used for pressurization. Examples of the gas used includeinert gas, steam, nitrogen gas, helium gas or the like. Pressurizationmay be regulated by a back pressure valve without a gas.

Heat treatment may be carried out using any method including, forexample, batch method, semi-batch method, flow-type reaction method orthe like. Among them, flow-type reaction method is preferable becausethe reaction time is easily regulated.

A time of heat treatment is preferably from 0.1 to 30 min, morepreferably from 0.2 to 15 min, even more preferably from 0.5 to 8 minafter the aqueous medium has reached the set temperature in view of anenhancement of solubility and a heat stability of the hardlywater-soluble polyphenols.

In the case of the flow-type reaction method, the time of the heattreatment is defined as the average residence time calculated from thevolume of the high temperature and high pressure part in the reactordivided by the supply rate of the aqueous medium.

In the case of the flow-type reaction method, the flow rate of theaqueous medium depends on the volume of the reactor. If the volume ofthe reactor is 100 mL, it is preferably from 3.3 to 200 mL/min, morepreferably from 6.7 to 150 mL/min.

After the heat treatment, it is preferable that the reaction solutionobtained by the heat treatment is cooled to 90° C. or lower, preferably50° C. or lower, more preferably 30° C. or lower. The lower limit ofcooling is 0° C. or higher, preferably 10° C. or higher, so that thereaction solution does not freeze. The reaction solution may be mixedand stirred for from 0.5 to 5 days, preferably from 1 to 3 days whilecooling. In addition, when a solid composition is to be obtained, thereaction solution may be subjected to a freeze-drying.

The cooling rate of the reaction solution, which is calculated from thetime required for lowering the temperature from the heat treatmenttemperature to 90° C., is 0.1° C./s or more, more preferably 0.2° C./sor more, more preferably 0.5° C./s or more, more preferably 1° C./s ormore, more preferably 3° C./s or more, even more preferably 5° C./s ormore. The solubility may be improved by larger cooling rate. Therefore,although the upper limit of the cooling rate is not particularlydetermined, it is preferably, for example, 100° C./s or less, morepreferably 50° C./s or less.

In addition, it is preferable to remove solid from the reaction solutionin order to increase the solubility of the composition obtained. Themethod to remove the solid is not particularly limited, and is carriedout, for example, by a centrifugation, a decantation or a filtration.

Although the polyphenol composition obtained by the first method has ahigh content of the hardly water-soluble polyphenols, a precipitation ofthe hardly water-soluble polyphenols is suppressed even at roomtemperature and the composition has the excellent solubility to water.In addition, the influence of the catechins, chlorogenic acids ormethylated product of hardly water-soluble polyphenols on the taste andflavor of the composition is small. Therefore, the polyphenolcomposition according to the present invention is applicable to variousfoods and drinks and pharmaceuticals or the like. It is especiallyuseful for packed beverage. Examples of the packed beverage include atea beverage such as green tea and a non-tea based beverage such assport drink, isotonic drink, near water, or the like.

Although the reason why the solubility of the hardly water-solublepolyphenols can be increased by the heat treatment of (A) hardlywater-soluble polyphenols and the component (B) at 100° C. or higher isnot clear, it is assumed as follows in accordance with the UV spectrumanalysis. It is supposed that the hardly water-soluble polyphenols, thecatechins, chlorogenic acids and methylated product of hardlywater-soluble polyphenols are solved in water by a self-association ofeach molecule having a structure in which the hydrophobic portion islaminated and the hydrophilic portion is faced outside, although thereis a difference in the solubility among the components. When heated at100° C. or higher in the state that the both components co-exist in theaqueous medium, the laminate structure may be collapsed anddisintegrated, causing the interaction between the hardly water-solublepolyphenols and the component (B) to form a new laminate structurecontaining the hardly water-soluble polyphenols and the component (B)intermixed. The solubility of the hardly water-soluble polyphenols maybe drastically enhanced because the new laminate structure is maintainedafter cooling.

A content of (A) hardly water-soluble polyphenols in the polyphenolcomposition obtained by the first method depends on a type of the hardlywater-soluble polyphenol, and it is preferably from 0.1 to 70%, morepreferably from 0.2 to 50%.

Although the hesperidin composition obtained by the second method has ahigh content of hesperidin, precipitation of hesperidin is suppressed atroom temperature, and the composition has the excellent solubility.

A solubility of hesperidin of the hesperidin composition is preferably1.3 g/L or more, more preferably 2 g/L or more, more preferably 3 g/L ormore, even more preferably 5 g/L or more. The solubility herein meansthe solubility to water at 25° C.

It has been previously known that α-glucosylhesperidin may be used asthe solubilizing agent for hesperidin. The solubilizing effect ofα-glucosylhesperidin has been limited, as described in Patent Document3. Therefore, the above-mentioned effect by the heat treatment at 100°C. or higher is considered to be a surprising effect which is notexpected from the conventional techniques.

Although the reason why the above-mentioned problem can be solved by theheat treatment of hesperidin and hesperidin sugar adduct at 100° C. orhigher is not clear, it is assumed as follows in accordance with the UVspectrum analysis. It is supposed that hesperidin and hesperidin sugaradduct are solved in water by a self-association of each molecule havinga structure in which the hydrophobic portion is laminated and thehydrophilic portion is faced outside, although there is a difference inthe solubility between both components. When heated at 100° C. or higherin the state that the both components co-exist in the aqueous medium,the laminate structure may be collapsed and disintegrated, causing theinteraction between hesperidin and hesperidin sugar adduct to form a newlaminate structure containing hesperidin and hesperidin sugar adductintermixed. The solubility of hesperidin may be drastically enhancedbecause the new laminate structure is maintained after cooling.

A mass ratio of hesperidin to hesperidin sugar adduct in the hesperidincomposition is from 0.3 to 10, preferably from 0.4 to 8, more preferablyfrom 0.5 to 8, even more preferably from 1 to 5.

A form of the polyphenol composition and the hesperidin compositionaccording to the present invention may be an aqueous solution, or apaste prepared by adjusting the content of water. In addition, thecomposition may be in a state of solid such as powder, granule, or solidby removing water. Means to adjust or remove the content of waterinclude freeze-drying, evaporation, spray-drying or the like.

EXAMPLES Measurement for Hardly Water-Soluble Polyphenols,Methylhesperidin and Hesperidin Sugar Adduct

A measurement for hardly water-soluble polyphenols, methylhesperidin andhesperidin sugar adduct was performed using High Performance LiquidChromatograph manufactured by Hitachi, Ltd. equipped with a columnCadenza CD-C18 (4.6 mmφ×150 mm, 3 μm) manufactured by Intact Co. at acolumn temperature of 40° C., in accordance with the gradient method. Amobile phase, Solution A, was 0.05 mol/L acetic acid aqueous solution,and another mobile phase, Solution B, was acetonitrile. Flow rate was1.0 mL/min. Gradient condition was as follows.

Time (min) Solution A (%) Solution B (%) 0 85 15 20 80 20 35 10 90 50 1090 50.1 85 15 60 85 15

Sample injection volume was 10 μL. Rutin and methylhesperidin weredetermined by absorbance at a wavelength of 360 nm. Ferulic acid andcaffeic acid were determined at 320 nm. Curcumin was determined at 425nm. Other hardly water-soluble polyphenols and hesperidin sugar adductwere determined at 283 nm.

[Measurement of Log P Value of the Hardly Water-Soluble Polyphenols]

The measurement was performed in accordance with the flask shakingmethod described in JIS 27260-107. First, 1-octanol and distilled waterwere shaken for 24 hours at 25° C. to equilibrate them. Then, 10 mg ofpolyphenol was weighed into a glass vial with a cap, into which each of4 mL of the equilibrated 1-octanol and water was added. The vial wasshaken for 4 days at 25° C. The phases of 1-octanol and water wereseparated by centrifugation, and the concentration of polyphenols ineach phase was determined by HPLC similarly to the above-mentioned“Measurement for hardly water-soluble polyphenols”. Log P value is acommon logarithm of the partition coefficient between the two phases.

[Measurement for the Catechins]

Samples were diluted with distilled water as needed, and were measuredusing a High Performance Liquid Chromatograph (Type SCL-10AVP)manufactured by Shimadzu Corporation equipped with a packed column forliquid chromatography L-Column TMODS (4.6 mmφ×250 mm: manufactured byJudicial Foundation Chemicals Evaluation and Research Institute, Japan),with a column temperature of 35° C., in accordance with the gradientmethod. A mobile phase, Solution A, was a distilled water solution of0.1 mol/L acetic acid, and another mobile phase, Solution B, was anacetonitrile solution of 0.1 mol/L acetic acid. Sample injection volumewas 20 μL, and the wavelength of UV detector was 280 nm.

(Concentration Gradient Condition)

Time (min) Solution A (% (v/v)) Solution B (% (v/v)) 0 97 3 5 97 3 37 8020 43 80 20 43.5 0 100 48.5 0 100 49 97 3 62 97 3[Measurement for Chlorogenic Acids](Analysis Apparatuses)

HPLC (manufactured by Hitachi, Ltd.) was used. Model numbers of thecomponent units of the apparatuses are as follows.

-   Solution sending unit (degasser included): L-2130-   Autosampler (with cooler): L-2200-   Column oven: L-2300-   Separation column: Cadenza CD-C18, Size: 4.6 mm i.d.×150 mm, 3 μm    (Intact Co.)-   Detector (UV-visible spectrophotometer): L-2420    (Analysis Conditions)-   Sample injection volume: 10 μL-   Flow rate: 1.0 mL/min-   Detection wavelength of UV spectrophotometer: 325 nm (for    chlorogenic acids)-   Eluent A: 5% acetonitrile containing 0.05 mol/L acetic acid, 0.01    mol/L sodium acetate, and 0.1 mmol/L HEDPO    Eluent B: Acetonitrile    (Concentration Gradient Condition)

Time (min) Solution A (% (v/v)) Solution B (% (v/v)) 0 100 0 10 100 0 1595 5 20 95 5 22 92 8 50 92 8 52 10 90 60 10 90 60.1 100 0 70 100 0

Example 1

Each of a hesperidin preparation (Hesperidin “Hamari” (trade name),manufactured by Hamari Chemicals Ltd., hesperidin content 90%, the sameshall apply hereafter) and an epigallocatechin gallate (EGCG)preparation (TEAVIGO manufactured by DMS Nutritional Products Co., EGCGcontent 100%, the same shall apply hereafter) was dispersed at aconcentration of 10 g/L and dissolved at a concentration of 4.29 g/L,respectively, in distilled water, and homogeneously stirred in a slurrysupply tank. The solution in the slurry supply tank was fed to astainless steel flow-type reactor with inner volume of 100 mL(manufactured by Nitto Koatsu Co., Ltd.) at a flow rate of 100 mL/min,and the reaction was carried out at 120° C. (average residence time 1minute). Pressure was adjusted to 0.3 MPa (gauge pressure) by an outletvalve. Reaction solution was taken out through the reactor outlet,cooled to room temperature (25° C.) and recovered. The recoveredsolution was stirred by shaking for 3 days at room temperature. Aftershaking, solid were filtered off to obtain the hesperidin composition asa hesperidin-containing aqueous solution. Reaction conditions and themeasurement result of a concentration of hesperidin and EGCG in thecomposition are shown in Table 1.

Example 2

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 1, except that the reactiontemperature was 110° C. Reaction conditions and the measurement resultof a concentration of hesperidin and EGCG in the composition are shownin Table 1.

Comparative Examples 1 and 2

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 1, except that the reactiontemperature was 90° C. or 70° C. and the gauge pressure was 0 MPa.Reaction conditions and the measurement result of a concentration ofhesperidin and EGCG in the composition are shown in Table 1.

Example 3

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 1, except that a purifiedcoffee bean extract (chlorogenic acids content 40%, the same shall applyhereafter) was used as the chlorogenic acids at a concentration of 10.7g/L. Reaction conditions and the measurement result of a concentrationof hesperidin and chlorogenic acids in the composition are shown inTable 1.

Comparative Example 3

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 3, except that the reactiontemperature was 70° C. and the gauge pressure was 0 MPa. Reactionconditions and the measurement result of a concentration of hesperidinand chlorogenic acids in the composition are shown in Table 1.

Example 4

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 1, except that amethylhesperidin preparation (manufactured by Hamari Chemicals Ltd.,methylhesperidin content 100%, the same shall apply hereafter) was usedinstead of the EGCG preparation. Reaction conditions and the measurementresult of a concentration of hesperidin and methylhesperidin in thecomposition are shown in Table 1.

Example 5

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 4, except that the reactiontemperature was 150° C. and the gauge pressure was 0.6 MPa. Reactionconditions and the measurement result of a concentration of hesperidinand methylhesperidin in the composition are shown in Table 1.

Comparative Examples 4 and 5

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 4, except that the reactiontemperature was 90° C. or 25° C. and the gauge pressure was 0 MPa.Reaction conditions and the measurement result of a concentration ofhesperidin and methylhesperidin in the composition are shown in Table 1.

Comparative Example 6

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 1, except that the EGCGpreparation was not added and that the reaction temperature was 25° C.and the gauge pressure was 0 MPa. Reaction conditions and themeasurement result of a concentration of hesperidin in the compositionare shown in Table 1.

TABLE 1 Comparative Comparative Comparative Example 1 Example 2 Example1 Example 2 Example 3 Example 3 Charge (A) Hardly Hesperidin HesperidinHesperidin Hesperidin Hesperidin Hesperidin water-soluble polyphenolslog P value of (A) −0.24 −0.24 −0.24 −0.24 −0.24 −0.24 Component (B)EGCG EGCG EGCG EGCG Chlorogenic Chlorogenic acid acid (A) Charged [g/L]9.00 9.00 9.00 9.00 9.00 9.00 concentration (B) Charged [g/L] 4.29 4.294.29 4.29 4.28 4.28 concentration (A)/(B) [—] 2.10 2.10 2.10 2.10 2.102.10 mass ratio Treatment Aqueous [—] water water water water waterwater Conditions medium Heating [° C.] 120 110 90 70 120 70 temperatureGauge [MPa] 0.3 0.3 0 0 0.3 0 pressure Analyzed value (A) [g/L] 1.030.92 0.14 0.14 0.95 0.09 concentration (25° C.) (B) [g/L] 4.20 4.22 4.194.19 4.16 4.13 concentration (25° C.) (A)/(B) [—] 0.245 0.218 0.0330.033 0.228 0.022 mass ratio Comparative Comparative Comparative Example4 Example 5 Example 4 Example 5 Example 6 Charge (A) Hardly HesperidinHesperidin Hesperidin Hesperidin Hesperidin water-soluble polyphenolslog P value of (A) −0.24 −0.24 −0.24 −0.24 −0.24 Component (B) Methyl-Methyl- Methyl- Methyl- — hesperidin hesperidin hesperidin hesperidin(A) Charged [g/L] 9.00 9.00 9.00 9.00 9.00 concentration (B) Charged[g/L] 4.29 4.29 4.29 4.29 — concentration (A)/(B) [—] 2.10 2.10 2.102.10 — mass ratio Treatment Aqueous [—] water water water water waterConditions medium Heating [° C.] 120 150 90 25 25 temperature Gauge[MPa] 0.3 0.6 0 0 0 pressure Analyzed value (A) [g/L] 2.12 2.7 0.67 0.050.05 concentration (25° C.) (B) [g/L] 4.19 4.15 4.22 4.24 —concentration (25° C.) (A)/(B) [—] 0.506 0.651 0.159 0.012 — mass ratio

Example 6

A quercetin composition was obtained as a quercetin-containing aqueoussolution by a same procedure as in Example 1, except that a quercetinpreparation (manufactured by Acros Organics Co., quercetin content 95%)was used as the hardly water-soluble polyphenols and that the reactiontemperature was 150° C. and the gauge pressure was 0.6 MPa. Reactionconditions and the measurement result of a concentration of quercetinand EGCG in the composition are shown in Table 2.

Comparative Example 7

A quercetin composition was obtained as a quercetin-containing aqueoussolution by a same procedure as in Example 6, except that the reactiontemperature was 70° C. and the gauge pressure was 0 MPa. Reactionconditions and the measurement result of a concentration of quercetinand EGCG in the composition are shown in Table 2.

Comparative Example 8

A quercetin composition was obtained as a quercetin-containing aqueoussolution by a same procedure as in Example 6, except that the EGCGpreparation was not added and that the reaction temperature was 25° C.and the gauge pressure was 0 MPa. Reaction conditions and themeasurement result of a concentration of quercetin in the compositionare shown in Table 2.

TABLE 2 Compar- Compar- ative ative Exam- Exam- Exam- ple 6 ple 7 ple 8Charge (A) Hardly water- quer- quer- quer- soluble cetin cetin cetinpolyphenols log P value of (A)  1.97 1.97 1.97 Component (B) EGCG EGCG —(A) Charged [g/L]  9.50 9.50 9.50 concentration (B) Charged [g/L]  4.294.29 — concentration (A)/(B) mass ratio [—]  2.21 2.21 — Treat- Aqueous[—] water water water ment medium con- Heating [° C.] 150 70 25 ditionstemperature Gauge pressure [MPa]  0.6 0 0 Anal- (A) concentration [g/L] 0.0116 0.0046 0.0046 yzed (25° C.) value (B) concentration [g/L]  4.204.20 — (25° C.) (A)/(B) mass ratio [—]  0.0028 0.0011 —

Example 7

A resveratrol composition was obtained as a resveratrol-containingaqueous solution by a same procedure as in Example 1, except that aresveratrol preparation (manufactured by Wako Pure Chemical Industries,Ltd., for biochemistry) was used as hardly water-soluble polyphenols ata concentration of 0.72 g/L. Reaction conditions and the measurementresult of a concentration of resveratrol and EGCG in the composition areshown in Table 3.

Comparative Example 9

A resveratrol composition was obtained as a resveratrol-containingaqueous solution by a same procedure as in Example 7, except that thereaction temperature was 70° C. and the gauge pressure was 0 MPa.Reaction conditions and the measurement result of a concentration ofresveratrol and EGCG in the composition are shown in Table 3.

Comparative Example 10

A resveratrol composition was obtained as a resveratrol-containingaqueous solution by a same procedure as in Example 7, except that theEGCG preparation was not added and that the reaction temperature was 25°C. and the gauge pressure was 0 MPa. Reaction conditions and themeasurement result of a concentration of resveratrol in the compositionare shown in Table 3.

TABLE 3 Compar- Compar- ative ative Example 7 Example 9 Example 10Charge (A) Hardly water- resveratrol resveratrol resveratrol solublepolyphenols log P value of (A) 3.08 3.08 3.08 Component (B) EGCG EGCG —(A) Charged [g/L] 0.72 0.72 0.72 concentration (B) Charged [g/L] 4.294.29 — concentration (A)/(B) mass ratio [—] 0.168 0.168 — Treat- Aqueousmedium [—] water water water ment Heating [° C.] 120 70 25 Con-temperature ditions Gauge pressure 0.3 0.3 0 0 [MPa] Anal- (A)Concentration [g/L] 0.128 0.060 0.058 yzed (25° C.) value (B)Concentration [g/L] 4.19 4.20 — (25° C.) (A)/(B) mass ratio [—] 0.0310.014 —

Example 8

A naringin composition was obtained as a naringin-containing aqueoussolution by a same procedure as in Example 1, except that a naringinpreparation (manufactured by Acros Organics Co., naringin content 97%,the same shall apply hereafter) was used as hardly water-solublepolyphenols and that the reaction temperature was 150° C. and the gaugepressure was 0.6 MPa. Reaction conditions and the measurement result ofa concentration of naringin and EGCG in the composition are shown inTable 4.

Example 9

A naringin composition was obtained as a naringin-containing aqueoussolution by a same procedure as in Example 8, except that the reactiontemperature was 110° C. and the gauge pressure was 0.3 MPa. Reactionconditions and the measurement result of a concentration of naringin andEGCG in the composition are shown in Table 4.

Comparative Examples 11 and 12

A naringin composition was obtained as a naringin-containing aqueoussolution by a same procedure as in Example 8, except that the reactiontemperature was 90° C. or 70° C. and the gauge pressure was 0 MPa.Reaction conditions and the measurement result of a concentration ofnaringin and EGCG in the composition are shown in Table 4.

Example 10

A naringin composition was obtained as a naringin-containing aqueoussolution by a same procedure as in Example 1, except that each of thenaringin preparation and the methylhesperidin preparation was dispersedat 5 g/L and dissolved at 4.29 g/L, respectively, in distilled water.Reaction conditions and the measurement result of a concentration ofnaringin and methylhesperidin in the composition are shown in Table 4.

Comparative Example 13

A naringin composition was obtained as a naringin-containing aqueoussolution by a same procedure as in Example 10, except that the reactiontemperature was 25° C. and the gauge pressure was 0 MPa. Reactionconditions and the measurement result of a concentration of naringin andmethylhesperidin in the composition are shown in Table 4.

Comparative Example 14

A naringin composition was obtained as a naringin-containing aqueoussolution by a same procedure as in Example 8, except that the EGCGpreparation was not added and that the reaction temperature was 25° C.and the gauge pressure was 0 MPa. Reaction conditions and themeasurement result of a concentration of naringin in the composition areshown in Table 4.

TABLE 4 Comparative Comparative Comparative Comparative Example 8Example 9 Example 11 Example 12 Example 10 Example 13 Example 14 Charge(A) Hardly water- naringin naringin naringin naringin naringin naringinnaringin soluble polyphenols log P value of (A) −0.15 −0.15 −0.15 −0.15−0.15 −0.15 −0.15 Component (B) EGCG EGCG EGCG EGCG methyl- methyl- —hesperidin hesperidin (A) Charged [g/L] 9.70 9.70 9.70 9.70 4.85 4.859.70 concentration (A) Charged [g/L] 4.29 4.29 4.29 4.29 4.29 4.29 —concentration (A)/(B) mass ratio [—] 2.26 2.26 2.26 2.26 1.13 1.13 —Treatment Aqueous medium [—] water water water water water water waterConditions Heating temperature [° C.] 150 110 90 70 120 25 25 Gaugepressure [MPa] 0.6 0.3 0 0 0.3 0 0 Analyzed value (A) concentration (25°C.) [g/L] 2.30 1.9 1.1 0.97 2.34 0.71 0.44 (B) concentration (25° C.)[g/L] 4.21 4.21 4.18 4.20 4.22 4.22 — (A)/(B) mass ratio [—] 0.55 0.450.27 0.23 0.55 0.17 —

Example 11

A curcumin composition was obtained as a curcumin-containing aqueoussolution by a same procedure as in Example 1, except that a curcuminpreparation (manufactured by Wako Pure Chemical Industries, Ltd.,special grade reagent) was used as hardly water-soluble polyphenols at aconcentration of 10 g/L and that the reaction temperature was 150° C.and the gauge pressure was 0.6 MPa. Reaction conditions and themeasurement result of a concentration of curcumin and EGCG in thecomposition are shown in Table 5.

Comparative Example 15

A curcumin composition was obtained as a curcumin-containing aqueoussolution by a same procedure as in Example 11, except that the reactiontemperature was 70° C. and the gauge pressure was 0 MPa. Reactionconditions and the measurement result of a concentration of curcumin andEGCG in the composition are shown in Table 5.

Comparative Example 16

A curcumin composition was obtained as a curcumin-containing aqueoussolution by a same procedure as in Example 11, except that the EGCGpreparation was not added and that the reaction temperature was 25° C.and the gauge pressure was 0 MPa. Reaction conditions and themeasurement result of a concentration of curcumin in the composition areshown in Table 5.

TABLE 5 Compar- Compar- Example ative ative 11 Example 15 Example 16Charge (A) Hardly water- curcumin curcumin curcumin soluble polyphenolslog P value of (A) 3.29 3.29 3.29 Component (B) EGCG EGCG — (A) Charged[g/L] 10.00 10.00 10 concentration (B) Charged [g/L] 4.29 4.29 —concentration (A)/(B) mass ratio [—] 2.33 2.33 — Treat- Aqueous medium[—] water water water ment Heating [° C.] 150 70 25 con- temperatureditions Gauge pressure [MPa] 0.6 0 0 Anal- (A) Concentration [g/L] 0.0140.001 0.001 yzed (25° C.) value (B) Concentration [g/L] 4.21 4.20 — (25°C.) (A)/(B) mass ratio [—] 0.0033 0.0002 —

Example 12

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 1, except that a rutin preparation(manufactured by Tokiwa Phytochemical Co., Ltd., rutin content 100%, thesame shall apply hereafter) was used as hardly water-soluble polyphenolsat a concentration of 2 g/L and that a purified green tea extract (anaqueous solution containing 15% of the catechins, a gallate forms ratio30%) was used as the catechins at a concentration of 28.6 g/L. Reactionconditions and the measurement result of a concentration of rutin andcatechins in the composition are shown in Table 6.

Comparative Example 17

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 12, except that the reactiontemperature was 70° C. and the gauge pressure was 0 MPa. Reactionconditions and the measurement result of a concentration of rutin andthe catechins in the composition are shown in Table 6.

Example 13

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 12, except that a purified coffee beanextract (chlorogenic acids content 40%) was used as chlorogenic acids ata concentration of 10.7 g/L. Reaction conditions and the measurementresult of a concentration of rutin and chlorogenic acids in thecomposition are shown in Table 6.

Comparative Example 18

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 13, except that the reactiontemperature was 70° C. and the gauge pressure was 0 MPa. Reactionconditions and the measurement result of a concentration of rutin andchlorogenic acids in the composition are shown in Table 6.

Example 14

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 12, except that a purified green teaextract (an aqueous solution containing 15% of the catechins, gallateforms ratio 30%) was used as the catechins at a concentration of 14.3g/L and that a purified coffee bean extract (chlorogenic acids content40%) was used as chlorogenic acids at a concentration of 5.4 g/L.Reaction conditions and the measurement result of a concentration ofrutin, the catechins and chlorogenic acids in the composition are shownin Table 6.

Comparative Example 19

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 14, except that the reactiontemperature was 70° C. and the gauge pressure was 0 MPa. Reactionconditions and the measurement result of a concentration of rutin, thecatechins and chlorogenic acids in the composition are shown in Table 6.

Example 15

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 12, except that a methylhesperidinpreparation was used at a concentration of 4.29 g/L instead of thepurified green tea extract. Reaction conditions and the measurementresult of a concentration of rutin and methylhesperidin in thecomposition are shown in Table 6.

Comparative Example 20

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 15, except that the reactiontemperature was 25° C. and the gauge pressure was 0 MPa. Reactionconditions and the measurement result of a concentration of rutin andmethylhesperidin in the composition are shown in Table 6.

Comparative Example 21

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 12, except that the catechins were notadded. Reaction conditions and the measurement result of a concentrationof rutin in the composition are shown in Table 6.

Comparative Example 22

A rutin composition was obtained as a rutin-containing aqueous solutionby a same procedure as in Example 12, except that the catechins were notadded and that the reaction temperature was 25° C. and the gaugepressure was 0 MPa. Reaction conditions and the measurement result of aconcentration of rutin in the composition are shown in Table 6.

TABLE 6 Comparative Comparative Comparative Example Example ExampleExample Example Example 12 17 13 18 14 19 Charge (A) Hardly rutin rutinrutin rutin rutin rutin water-soluble polyphenols log P value of (A)−0.33 −0.33 −0.33 −0.33 −0.33 −0.33 Component (B) purified purifiedchlorogenic chlorogenic purified purified green tea green tea acid acidgreen tea green tea extract extract extract + extract + chlorogenicchlorogenic acid acid Charged [g/L] 2.00 2.00 2.00 2.00 2.00 2.00concentration of (A) Charged [g/L] 4.29 4.29 4.28 4.28 4.31 4.31concentration of (B) (A)/(B) mass [—] 0.47 0.47 0.47 0.47 0.46 0.46ratio Treatment Aqueous medium [—] water water water water water waterconditions Heating [° C.] 120 70 120 70 120 70 temperature Gaugepressure [MPa] 0.3 0 0.3 0 0.3 0 Analyzed value (A) [g/L] 0.135 0.0440.105 0.057 0.13 0.08 concentration (25° C.) (B) [g/L] 4.19 4.19 4.174.14 4.18 4.18 concentration (25° C.) (A)/(B) mass [—] 0.0322 0.01050.025 0.014 0.031 0.019 ratio Comparative Comparative ComparativeExample Example Example Example 15 20 21 22 Charge (A) Hardly rutinrutin rutin rutin water-soluble polyphenols log P value of (A) −0.33−0.33 −0.33 −0.33 Component (B) methyl- methyl- — — hesperidinhesperidin Charged [g/L] 2.00 2.00 2.00 2.00 concentration of (A)Charged [g/L] 4.29 4.29 — — concentration of (B) (A)/(B) mass [—] 0.470.47 — — ratio Treatment Aqueous medium [—] water water water waterconditions Heating [° C.] 120 25 120 25 temperature Gauge pressure [MPa]0.3 0 0.3 0 Analyzed value (A) [g/L] 0.28 0.07 0.037 0.028 concentration(25° C.) (B) [g/L] 4.21 4.24 — — concentration (25° C.) (A)/(B) mass [—]0.067 0.017 — — ratio

Example 16

A ferulic acid composition was obtained as a ferulic acid-containingaqueous solution by a same procedure as in Example 1, except that aferulic acid preparation (manufactured by Tokyo Chemical Industry Co.,Ltd., ferulic acid content 100%) was used as hardly water-solublepolyphenols at a concentration of 6 g/L and that a purified coffee beanextract was used as chlorogenic acids at a concentration of 10.7 g/L.Reaction conditions and the measurement result of a concentration offerulic acid and chlorogenic acid in the composition are shown in Table7.

Comparative Examples 23 and 24

A ferulic acid composition was obtained as a ferulic acid-containingaqueous solution by a same procedure as in Example 16, except that thereaction temperature was 70° C. or 25° C. and the gauge pressure was 0MPa. Reaction conditions and the measurement result of a concentrationof ferulic acid and chlorogenic acid in the composition are shown inTable 7.

TABLE 7 Compar- Compar- ative ative Exam- Exam- Exam- ple 16 ple 23 ple24 Charge (A) Hardly water- ferulic ferulic ferulic soluble acid acidacid polyphenols log P value of (A) 1.51  1.51 1.51 Component (B)chloro- chloro- chloro- genic genic genic acid acid acid (A) Charged[g/L] 6.00  6.00 6.00 concentration (B) Charged [g/L] 4.28  4.28 4.28concentration (A)/(B) mass ratio [—] 1.40  1.40 1.40 Treat- Aqueousmedium [—] water water water ment Heating [° C.] 120 70 25 con-temperature dition Gauge pressure [MPa] 0.3  0 0 Anal- (A) Concentration[g/L] 6.00  2.42 1.61 yzed (25° C.) value (B) Concentration [g/L] 4.19 4.16 4.16 (25° C.) (A)/(B) mass ratio [—] 1.43  0.58 0.39

Example 17

A caffeic acid composition was obtained as a caffeic acid-containingaqueous solution by a same procedure as in Example 1, except that acaffeic acid preparation (manufactured by Tokyo Chemical Industry Co.,Ltd., caffeic acid content 100%) was used as hardly water-solublepolyphenols at a concentration of 6 g/L and that a purified coffee beanextract was used as chlorogenic acids at a concentration of 10.7 g/L.Reaction conditions and the measurement result of a concentration ofcaffeic acid and chlorogenic acid in the composition are shown in Table8.

Comparative Examples 25 and 26

A caffeic acid composition was obtained as a caffeic acid containingaqueous solution by a same procedure as in Example 17, except that thereaction temperature was 80° C. or 25° C. and the gauge pressure was 0MPa. Reaction conditions and the result of the measurement ofconcentration of caffeic acid and chlorogenic acid in the compositionare shown in Table 8.

TABLE 8 Compar- Compar- ative ative Exam- Exam- Exam- ple 17 ple 25 ple26 Charge (A) Hardly water- caffeic caffeic caffeic soluble acid acidacid polyphenols log P value of (A) 1.15 1.15 1.15 Component (B) chloro-chloro- chloro- genic genic genic acid acid acid (A) Charged [g/L] 6.006.00 6.00 concentration (B) Charged [g/L] 4.28 4.28 4.28 (A)/(B) mass[—] 1.40 1.40 1.40 concentration ratio Treat- Aqueous medium [—] waterwater water ment Heating [° C.] 120 80 25 con- temperature ditions Gaugepressure [MPa] 0.3 0 0 Anal- (A) [g/L] 6.00 2.79 0.88 yzed Concentrationvalue (25° C.) (B) [g/L] 4.16 4.13 4.16 Concentration (25° C.) (A)/(B)mass [—] 1.44 0.68 0.21 ratio

As is clearly shown in Tables 1 to 8, it was possible to obtain thepolyphenol composition with a high content of hardly water-solublepolyphenols, whereby significant increase of the solubility of hardlywater-soluble polyphenols has been achieved.

Furthermore, the compositions obtained had no strange odor such as grainsmell. The compositions including the catechins and chlorogenic acidshad a moderate bitterness derived from these components. They also had ataste and flavor suitable for various foods and drinks andpharmaceuticals, especially for functional beverages.

Example 18

Each of a hesperidin preparation and a monoglucosylhesperidinpreparation (Hayashibara Hesperidin S (trade name), manufactured byHayashibara Biochemical Laboratories, Inc., hesperidin content 17mass %,monoglucosylhesperidin content 74 mass %, the same shall applyhereafter) was dispersed at a concentration of 10.0 g/L and dissolved ata concentration of 4.3 g/L, respectively, in distilled water, andhomogeneously stirred in a slurry supply tank. The solution in theslurry supply tank was fed to a stainless steel flow-type reactor withinner volume of 100 mL (manufactured by Nitto Koatsu Co., Ltd.) at aflow rate of 100 mL/min, and the reaction was carried out at 120° C.(average residence time 1 minute). Pressure was adjusted to 1.5 MPa byan outlet valve. Reaction solution was taken out through the reactoroutlet, cooled to room temperature (25° C.) and recovered to a reactionsolution recovery tank. The cooling was performed by a continuous heatexchange with coolant water, passing the reaction solution taken outthrough the outlet of the flow-type reactor to a dual pipe cooler.

The recovered reaction solution was stirred for 3 days at roomtemperature. Solids were then filtered off to obtain the hesperidincomposition as a hesperidin-containing aqueous solution. Reactionconditions and the measurement result of a concentration of hesperidin(HES) and monoglucosylhesperidin (mGHES) in the composition are shown inTable 9 (the same shall apply hereafter).

Example 19

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 18, except that the reactiontemperature was 150° C. In addition, a powdery hesperidin compositionwas obtained by a freeze-drying to remove water. It has found that thepowdery hesperidin composition redissolves in water (25° C.) even at aconcentration of 10 g/L.

Example 20

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 18, except that the reactiontemperature was 180° C.

Example 21

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 19, except that aconcentration of the monoglucosylhesperidin preparation in distilledwater was 1.1 g/L.

Example 22

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 19, except that aconcentration of the hesperidin preparation in distilled water was 20g/L.

Comparative Example 27

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 18, except that the reactiontemperature was 25° C.

Comparative Example 28

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 18, except that the reactiontemperature was 90° C.

Example 23

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 18, except that aconcentration of the monoglucosylhesperidin preparation in distilledwater was 10 g/L.

Example 24

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 23, except that the reactiontemperature was 150° C.

Example 25

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 23, except that the reactiontemperature was 180° C.

Comparative Example 29

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 23, except that the reactiontemperature was 90° C.

The mass ratio of HES relative to mGHES in the hesperidin compositionobtained in Examples 18 to 25 and Comparative Examples 27 to 29 is shownin Table 9.

TABLE 9 Compar- Compar- Compar- Exam- Exam- Exam- Exam- Exam- Exam-Exam- Exam- ative ative ative ple ple ple ple ple ple ple ple ExampleExample Example 18 19 20 21 22 23 24 25 27 28 29 Charge Hesperidin [g/L]10.0 10.0 10.0 10.0 20.0 10.0 10.0 10.0 10.0 10.0 10.0 preparation*monoglucosyl- [g/L] 4.3 4.3 4.3 1.1 4.3 10.0 10.0 10.0 4.3 4.3 10.0hesperidin preparation** Treatment Aqueous [—] water water water waterwater water water water water water water conditions medium Temperature[° C.] 120 150 180 150 150 120 150 180 25 90 90 Pressure [MPa] 1.5 1.51.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Analyzed HES [g/L] 2.29 2.11 2.081.31 3.07 3.06 3.04 2.86 0.46 0.65 1.28 value mGHES [g/L] 3.04 2.18 2.140.41 1.85 7.37 5.80 5.54 3.25 3.09 7.31 HES/mGHES [g/g] 0.75 0.97 0.973.21 1.67 0.42 0.52 0.52 0.19 0.21 0.17 *Hesperidin “Hamari” (tradename), Hamari Chemicals, Ltd. **Hayashibara Hesperidin S (trade name),Hayashibara Biochemical Laboratories, Inc.

As is clearly shown in Table 9, it was possible to obtain the hesperidincomposition with a high content of hesperidin by a heat treatment ofhesperidin and hesperidin sugar adduct at from 100 to 180° C., wherebysignificant increase of the solubility of hesperidin has been achieved.

Example 26

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 19, except that a 50 vol %aqueous ethanol solution was used instead of distilled water as theaqueous medium to disperse the hesperidin preparation or to dissolve themonoglucosylhesperidin preparation. The measurement result of aconcentration of HES and mGHES in the composition is shown in Table 10(the same shall apply hereafter).

Comparative Example 30

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 26, except that the reactiontemperature was 25° C.

The mass ratio of HES relative to mGHES in the hesperidin compositionobtained in Example 26 and Comparative Example 30 is shown in Table 10.

TABLE 10 Example Comparative 26 Example 30 Charge Hesperidin [g/L] 10.010.0 preparation * Monoglucosylhesperidin [g/L] 4.3 4.3 preparation **treatment Aqueous medium [—] 50 vol % 50 vol % conditions ethanolethanol Temperature [° C.] 150 25 Pressure [MPa] 1.5 1.5 Analyzed HES[g/L] 5.13 0.48 value mGHES [g/L] 3.01 3.01 HES/mGHES [g/g] 1.71 0.16 *Hesperidin “Hamari” (trade name) Hamari Chemicals, Ltd. ** HayashibaraHesperidin S (trade name), Hayashibara Biochemical Laboratories, Inc.

As is clearly shown in Table 10, it was possible to obtain thehesperidin composition with a high content of hesperidin by using anaqueous solution containing an organic solvent as the aqueous medium forthe reaction.

Example 27

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 18, except that a soy sauce(pH 4.9, manufactured by Yamasa Corporation) was used instead ofdistilled water. The measurement result of a concentration of HES andmGHES in the composition is shown in Table 11 (the same shall applyhereafter).

Example 28

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 18, except that a low-saltsoy sauce (pH 4.7, manufactured by Yamasa Corporation) was used insteadof distilled water and that the pressure was 0.3 MPa.

Example 29

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a same procedure as in Example 18, except that a seasonedponzu sauce (pH 2.0, manufactured by Mizkan Group Corporation) was usedinstead of distilled water and that the pressure was 0.3 MPa.

TABLE 11 Example Example Example 27 28 29 Charge Hesperidin [g/L] 10.010.0 10.0 preparation * Monoglucosylhesperidin [g/L] 4.3 4.3 4.3preparation ** Treatment Aqueous medium [—] soy low-salt ponzuconditions sauce soy sauce sauce Temperature [° C.] 120 120 120 Pressure[MPa] 1.5 0.3 0.3 Analyzed HES [g/L] 1.97 2.87 2.06 value mGHES [g/L]3.02 3.04 3.07 HES/mGHES [g/g] 0.65 0.94 0.67 * Hesperidin “Hamari”(trade name), Hamari Chemicals, Ltd. ** Hayashibara Hesperidin S (tradename), Hayashibara Biochemical Laboratories, Inc.

As is clearly shown in Table 11, it was also possible to obtain thehesperidin composition with a high content of hesperidin by using anaqueous medium containing a solute such as amino acid or a salt.

Example 30

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a similar procedure as in Example 18, except that thepressure was 0.3 MPa. The cooling rate was 7.06° C./s by calculating thecooling time from 120° C. to 90° C. The measurement result of aconcentration of HES and mGHES in the composition is shown in Table (thesame shall apply hereafter).

Example 31

A hesperidin composition was obtained as a hesperidin-containing aqueoussolution by a similar procedure as in Example 30, except that thetemperature and flow rate of the cooling water was changed so that thecooling rate calculated from the cooling time from 120° C. to 90° C. wasadjusted to 0.52° C./s.

TABLE 12 Example Example 30 31 Charge Hesperidin [g/L] 10.0 10.0preparation * monoglucosylhesperidin [g/L] 4.3 4.3 preparation **Treatment Aqueous medium [—] water water conditions Temperature [° C.]120 120 Pressure [MPa] 0.3 0.3 Cooling rate [° C./s] 7.06 0.52 AnalyzedHES [g/L] 2.82 1.11 value mGHES [g/L] 3.04 2.73 HES/mGHES [g/g] 0.930.41 * Hesperidin “Hamari” (trade name), Hamari Chemicals, Ltd. **Hayashibara Hesperidin S (trade name), Hayashibara BiochemicalLaboratories, Inc.

The invention claimed is:
 1. A method for producing a polyphenolcomposition comprising subjecting: (A) a hardly water-soluble polyphenolwhich is at least one member selected from the group consisting ofhesperidin, quercetin, resveratrol, naringin, curcumin, rutin, caffeicacid and ferulic acid, and (B) at least one member selected from thegroup consisting of chlorogenic acids and methylated compounds of hardlywater-soluble polyphenols to a heat treatment at from 100 to 180° C. inthe presence of an aqueous medium.
 2. The method for producing thepolyphenol composition according to claim 1, wherein the heat treatmentis carried out at a temperature of from 110 to 170° C.
 3. The method forproducing the polyphenol composition according to claim 1, wherein amass ratio (A)/(B) is from 0.005 to 10 in the heat treatment.
 4. Themethod for producing the polyphenol composition according to claim 3,wherein the methylated compound of the hardly water-soluble polyphenolis present and is methylhesperidin.
 5. The method for producing thepolyphenol composition according to claim 1, further comprising: coolinga reaction solution obtained by the heat treatment and removing a solidfrom the cooled reaction solution.